Process for preparing edible fat compositions containing triglycerides derived from c16,c18,c20,and c22 fatty acids

ABSTRACT

AN EDIBLE UNRANDOMISED FAT BLEND PREPARED FROM HARDENED OILS AND CONTAINING FROM 10 TO 50% OF A COMPONENT A WHOSE TRIGLYCERIDES HAVE A C16 AND 18 ACID CONTENT OF AT LEAST 90%, OF WHICH FROM 10 TO 45% ISSATURATED ACID, AND FROM 50 TO 90% OF A COMPONENT B WHOSE TRIGLYCERIDES HAVE A C20 AND 22 ACID CONTENT OF FROM 30 TO 75% AND NOT MORE THAN 20% SATURATED ACID, BOTH COMPONENTS HAVING A C18 MONOETHENOIC RADICAL IN AT LEAST 85% OF THE GLYCERIDE 2-POSITIONS AND A TRANS INDEX OF BETWEEN 40 AND 75, SHOWS INTERACTION OF THE COMPONENTS RESULTING IN IMPROVEMENT OF MELTING CHARACTERISTICS WHICH MAKE THE BLEND SUITABLE AS A REPLACEMENT FOR LAURIC FATS.

Dec. 19, 1972 B. CAVERLY ETAL 3,706,576

PROCESS FOR PREPARING EDIBLE FAT COMPOSITIONS CONTAINING TRIGLYCERIDESDERIVED FROM 0,, c, 0 AND 0 FATTY ACIDS Original Filed Nov. 14, 1968 4Sheets-Sheet 1 FIG].

A2 +0 1'0 2'0 3b in s'u- 5'0 7'0 ab sin 100 mu 50 n-a2 INVENTORS:

BRIAN LEONARD CAVERLY 8 JOHN BARRY ROSSELL Dec. 19, 1972 B. L. CAVERLYEIAL 3,706,576

PROCESS FOR PREPARING EDIBLE FAT COMPOSITIONS CONTAINING TRIGLYCERIDESDERIVED FROM Cm 0, AND 0 FATTY ACIDS Original Filed Nov. 14, 1968 4Sheets-Sheet 2 0061420005142 3310332222 U nU a d-H.7 mnw OOrU ZOODrU/q.333332 22 a w I 1U 2U Ll] .51] 8U INVENTORS:

BRIAN LEONARD CAVERLY 8s JOHN BARRY ROSSELL BY T ElR A Dec. 19. 19725.1.. CAVERLY ET L 3,703,576

PROCESS FOR PREPARING EDIBLE FAT COMPOSITIONS CONTAINING TRIGLYCERIDESDERIVED FROM a 0 C AND C FATTY ACIDS 4 Sheets-Sheet 3 Original FiledNov. 14 1968 FIGS.

INVENTORS:

BRIAN LEONARD CAVERLY 8 JOHN BARRY RUSSELL BY THEIR ATTORNEY B. L.CAVERLY ETA!- Dec. 19, 1972 3,,?@6,576

PROCESS FOR PREPARING EDIBLE FAT COMPOSITIONS CONTAINING TRIGLYCERIDESDERIVED FROM c, 0, 0 AND 0 FATTY ACIDS 4 Sheets-Sheet 4 Original FiledNov. 14 1968 ab so 100 owns 1U 2U 3U 40 l l' 10 20 an an 50 5b in 8b901m] 50 INVENTORS 1 BRIAN LEONARD CAVERLY a JQHN BARRY ROSSELL egggmUnited States Patent PROCESS FOR PREPARING EDIBLE FAT COMPO- SITIONSCONTAINING TRIGLYCERIDES DE- RIVED FROM C C C AND C FATTY AClDS BrianLeonard Caverly, Meopham, and John Barry Rossell, St. Albans, England,assignors to Lever Brothers Company, New York, N.Y.

Continuation of abandoned application Ser. No. 775,728, Nov. 14, 1968.This application Aug. 9, 1971, Ser. No. 170,382

Claims priority, application Great Britain, Nov. 20, 1967,

52,780/67 Int. Cl. A23d 5/00 U.S. Cl. 99-118 R 14 Claims ABSTRACT OF THEDISCLOSURE An edible unrandomised fat blend prepared from hardened oilsand containing from to 50% of a component A whose triglycerides have a Cand C acid content of at least 90%, of which from 10 to 45% is saturatedacid, and from 50 to 90% of a component B whose triglycerides have a Cand C acid content of from to 75% and not more than 20% saturated acid,both components having a C monoethenoic radical in at least 85% of theglyceride 2-positions and a trans index of between 40 and 75, showsinteraction of the components resulting in improvement of meltingcharacteristics which make the blend suitable as a replacement forlauric fats.

This application is a continuation of application Ser. No. 775,728, Nov.14, 1968, now abandoned.

This invention relates to a process for preparing edible fats and toedible fat compositions.

Coconut and palm kernel oils are used in the manufacture of fats thatare solid at normal temperatures but are liquid at body temperature andhence melt in the mouth on consumption. The conversion of these oils tosuch fats is effected by hardening with hydrogen and a hydrogenationcatalyst. These fats contain large amounts of lauric acid astriglycerides and show a tendency to develop oil-flavours becausedeterioration on storage frees lauric acid and shorter-chain acids whosepresence is easy to detect by their unpleasant taste in comparison withacids in other fats, for instance stearic and palmitic acids.

On the other hand many natural oils whose glycerides are free fromlauric acid, on hardening to a fat that is adequately firm at 20 C.,give a product that is unsatisfactory as a general purpose fat becausetheir content of high-melting glycerides is such that they do not meltreadily in the mouth, and resort must be had to fractionation to removea tail of high-felting, waxy material. Many selectively hardened oils,for instance hardened cottonseed oil, show this disadvantage.

A method has now been found of upgrading certain hardened oils of thiskind, by which the hardened oils are blended with other hardened oilsand the tail is reduced or made to disappear as a result of anunexpected eifect. The resulting fats are without the disadvantage dueto the presence of lauric acid, and can be used as general purpose fats.

The melting properties of fats are now commonl defined by theirdilatations at the temperatures concerned, dilatation being theisothermal melting expansion expressed in cubic millimetres and referredto 25 grams of material. The standard method of measuring dilatationsfor the purposes of this specification is that described in British Pat.827,172. The dilatation of a fat gives an indication of the solidscontent of the fat at a particular temperature within its melting range.Dilatation curves can be drawn in which dilatation values are plottedagainst ice temperature, for instance for temperature ranges from 15 to45 C. The steeper the curve the shorter is the range of temperaturesbetween which the fat is essentially solid and liquid respectively.

Where a comparison of the melting properties of fats prepared byblending two component fats in various proportions is required, a seriesof superimposed dilatation curves for difierent compositions is usuallyunsatisfactory, because they differ in steepness and obscure one anotherby intersection. It has instead been found convenient to illustrate themelting properties of the blends by plotting dilatation curves,establishing the temperatures at which a series of blends in differentproportions of the two components have a particular dilatation value,plotting these temperatures against blend compositions, and joining thepoints showing that dilatation value. The resulting curve is designatedan isodilatation curve. The influence of blend composition on meltingproperties is then illustrated by a series of curves drawn for a seriesof dilatation values, for instance 50, 100, 200, 500, 800, 1000, 1200and 1400 covering a complete range from solid fats to molten fats. Asthe resulting curves generally do not intersect, conclusions may morereadily be drawn. The graph containing such a series of curves isdesignated as isodilatation diagram, and presents a contour map in whicheach contour is a line of equal dilatation value, and the closeness ofthe contours for any given composition indicates the steepness of thedilatation curve for that composition. It is therefore possible,provided sufiicient curves are drawn, to obtain from the diagram thedilatation at any particular temperature, as well as the steepness ofthe dilatation curve, representing the sharpness of melting, for allcompositions of blend, using interpolation where necessary.

Such an isodilatation diagram is shown in FIG. 1 of the accompanyingdrawings, in which blends of from 0 to 100% of the selectivelyhydrogenated liquid palm oil (palm oleine) fraction A1 of Example 1 (seebelow) and from 100 to 0% of the selectively hydrogenated rapeseed oil Bof Example 1, and temperature T in C. are represented by the axes andthe isodilatation curves D are given for the series of dilatation valuesmentioned above. FIG. 1 reveals an unexpected maximum in theisodilatation curves at a *blend of about 25% Al and B1, the maximumbeing very pronounced at low temperatures (see D=1400 isodilatationcurve) and becoming less pronounced with increasing temperatures. Whileeutectic behaviour in isodilatation curves is normal with oil blends andFIG. 1 shows minima representing this behaviour, the neighbouring maximatake a form that suggest some kind of interaction or association betweena large proportion of the glyceride molecules of one component and alarge proportion of the glyceride molecules of the other, perhaps of thenature of a molecule compound. This is supported by the fact that ifeach component is interesterified before blending, the maxima disappear.The discovery of such maxi-ma is important, as they represent propertiesunexpected from the properties of the blend components.

FIG. 1 shows that blends containing from 10' to 50% of A1 and to 50% ofB1 exhibit an isodilatation maximum especially at about 20 C., implyingthat their solids content is unexpectedly high at this temperature. Onthe other hand the minimum temperature at which such blends are whollyliquid is lower than would be accounted for by an interpolation of theproperties of the components. This means that while the A1 component isunsatisfactory as a fat by itself, as it does not melt fully in themouth, and the B1 component is not completely satisfactory by itself asit is not rigid enough at low temperatures for some purposes, the blendsrepresented by the isodilatation maximum are satisfactory at both endsof the temperature range, and more satisfactory at each end than couldhave been predicted.

Differential thermal analysis of some of the compositions whosedilatations are represented in FIG. 1 has shown that a comparablemaximum in latent heat of fusion of the blends also occurs, thusproviding further evidence of the interaction.

The isodilatation diagrams for the following blends of oils described inthe examples below and shown in FIGS. 2 to 7 of the accompanyingdrawings also reveal the new interaction phenomenon in a similar manner.

Figure Fat Component A Fat Component B 2 Selectively hydrogenatedSelectively hydrogenated cottonseed oil A2. rapeseed oil B2.

3 Selectively hydrogenated Selectively hydrogenated groundnut oil A3.rapeseed oil B3.

4 Stearine fraction A41rom Stearine fraction B4 from selectivelyhydrogenated selectively hydrogenated zero-erucie rapeseed oil. rapeseedoil.

5 Stearine fraction A5 from Stearine traction B5 from selectivelyhydrogenated selectively hydrogenated cottonseed oil. rapeseed oil.

6 Stearine fraction A4 from Stearine fraction B5 from selectivelyhydrogenated selectively hydrogenated zero-erucic rapeseed oil. crambeoil.

7 Selectively hydrogenated Selectively hydrogenated palm oleine fractionA6. oleine fraction B7 from selectively hydrogenated rapeseed oil.

In every instance the isodilatation curves reveal maxima.

Fats can exist in a variety of crystalline polymorphic forms, includingthose known as the alpha, beta and beta prime forms: these havedifferent stability, melting point and density characteristics. Theparticular form in which a given fat crystallises depends not only onits glyceride composition, but on the temperature and rate ofcrystallisation. The polymorphic form of a crystalline fat can bedetermined by means of its X-ray powder diffraction pattern, and theabove fat components and their blends have been submitted to thisdetermination. It has been found that while the polymorphic form of fatcomponents B present when dilatation measurements are made is a betaprime form, the fats change slowly over several weeks to a stable betaform. The polymorphic form of the fat components A present whendilatations measurements are made is the beta prime form; this is alsousually the stable form, and component A4, where the stable form is thebeta form, is exceptional. The polymorphic form of a blend of fatcomponents A and B corresponding to the maxima in the isodilatationcurves is beta prime when dilatation measurements are made, and this isalso the stable form for that blend. Where the amount of fat component Ais more than that corresponding to the isodilatation maxima, the blendis also stable in the beta prime form: however, where the amount of fatcomponent A is less than that corresponding to the isodilatationmaximum, the blend is unstable in the beta prime form, and slowtransformation to the beta form takes place, the transformation beingless slow as the content of fat component B is increased.

These polymorphic states are summarised in the following table.

Form during dilatation measurement Stable form Beta prime Beta prime orbeta.

do. Bet

B a. Blend corresponding to do Beta prime.

isodilatation maximum.

and 3-positions of the glyceryl radicals in the triglyceride moleculesin such a way that when the fats are blended interaction occurs betweentwo types of triglyceride molecules present, one type being provided bythe fat component A and the other by the fat component B. It may be thatas in general the fat component A has a high content of PEE and PEPglycerides (P being -a palmitic acid radical and E an elaidic acid typeradical, that is, elaidic acid or its trans double bond-positionalisomers) and the fat component B has a high content of BrEBr and 'BrEEglycerides (Br being a brassidic acid type radical), the interaction iscaused by association between one or more pairs of these glycerides, andthat this interaction involves only the beta prime form of theglycerides, with the tendency of the glycerides from the fat component Bto go over to the beta form being completely suppressed in blends withamounts of the fat components A above those corresponding to thedilatation maxima. Such blends thus have a relatively simple polymorphicbehaviour, the transformation from a beta prime to a beta form beinginhibited: this is advantageous in edible fats, for this type oftransformation can lead to bloom on chocolate goods and graininess orsandiness in softer fats, for instance, those used as biscuit fillingcreams.

The preparation of fats showing this interaction requires a mixing step,before or after hardening, of natural fats or fat fractions, as theycannot be obtained by direct hydrogenation and isomerisation ofunblended natural fats with or without subsequent fractionation, for theproportions and distribution of the various fatty acid radicals areunsuitable; nor can they be obtained from interesterified fats, whetherby interesterification of mixed fats or mixing of interesterified fats,for interesterification results in a random distribution of the acidradicals among the three positions of the glyceryl radical.

In a process of this invention an edible fat composition is prepared byforming a blend of from 10 to by weight of an unrandomised fat componentA the total fatty acids of Whose triglycerides have a C 'and C acidcontent of at least 90% by weight, of which from 10 to 45% is saturatedfatty acid, and from 50 to 90% of an unrandomised fat component B thetotal fatty acids of whose triglycerides have a C and C acid content offrom 30 to 75% by weight and not more than 20% of saturated fatty acid,both components A and B having at least 85% of the 2-positions occupiedby a C monoethenoic acid radical, and a trans index of between 40 and75.

By unrandomised fat is meant a fat of natural origin which has beensubmitted to the required isomerisation step with or Withouthydrogenation and fractionation, but without randomisation byinteresterification, and retains the original distribution of chains ofcarbon atoms in the acid radicals within its triglyceride molecules. Thenature and proportion of fatty acid radicals present at the 2- positionsof the triglycerides in a fat can be determined by submitting the fat tolipase hydrolysis, which leaves the radicals at the 2-positionunhydrolysed, removing the I free acids formed and then liberating the2-position acids by saponification and analysing them by standardmethods. By trans index is meant the apparent trans content percent ofthe fatty acids providing the acid radicals of the triglyceridesmeasured by the recommended method described in J. Amer. Oil ChemistsSoc., 1959, 36, 627- 31, and calculated as methyl elaidate.

In practice the stable polymorphic form of the fat component B is beta,and that of the fat component A is beta, or more usually, beta prime.

Preferably at least of the Z-positions in the triglycerides of both fatcomponents A and B are occupied by a C monoethenoic acid radical.Preferably the fat component A has from 15 to 40% of saturated C and Cacids by weight of the total acids and preferably it has not more than6% of other saturated fatty acids. Preferably it has a trans index ofbetween 40 and 60.

Preferably the fat component B has at least 40%, and especially at least50% of C and C acids; and preferably of these the C acid predominates,for instance at least 75% of such acids is C acid. Preferably thecomponent B has a trans index of between 50 and 70. Preferably the fatcomponent B has less than 12% of saturated fatty acid, and of thispreferably substantially all is C and C acids. Preferably the transindex of the blend of fat components is between 50 and 70.

Preferably the temperatures at which the fat components A and B have aparticular dilatation within the range of 750 to 1250, for instance 800,1000 or 1200, are less than 15, especially less than 10, apart, so thatthe tendency for phase separation of component triglycerides thatinteract is reduced. In practice both components A and B havedilatations at 20 C. of at least 1000, preferably that of A is at least1200; and the dilatation of the fat blend at 20 C. is at least 1050.

The presence in the blend of large amounts of polyethenoic acids isdetrimental, and there should in practice be less than 10 and preferableless than 5% of them in the total fatty acids of either fat component.Preferably the fat component A has an iodine value of between 50 and 75,the fat component B one of between 65 and 80, and the composition one ofbetween 50 and 80, especially between 60 and 76. The partial glyceridecontent of the blend should preferably be as low as possible.

Preferably the proportion of fat component A in the blend is such thatthe stable polymorphic form of the blend is beta prime; alternatively itis such that it is within of that providing a maximum in theisodilatation curve of mixtures of fat components A and B for adilatation of 1200, and preferably is that providing the maximum.

In one form of process according to the invention the blend of fatcomponents A and B is formed directly by mixing the separate components.Mixing is in practice effected by adding together the components in theliquid state. An individual fat component can be prepared by selectivelyhardening to the required extent a natural oil containing polyethenoicacids in its triglycerides with isomerisation of cis acids to transacids, followed if desired by fractionation; or a natural oil can befractionated and then selectively hardened, with further fractionationif desired.

The conditions, including nature and quantity of catalyst, temperatureand pressure, for a hydrogenation selective for the hardening ofpolyethenoic acids (which include diethenoic acids) to monoethenoicacids, are wellknown. Conventional catalysts employed in suchhydrogenations are conducive to the isomerisation of cis-ethenoic acidsto trans-ethenoic acids, and a separate isomerisation step isunnecessary using them, but if isomerisation is required to bring thetrans index of the hardened oil to the required value, the oil can beheated with an isomerising catalyst. It is convenient to use asulphurised nickel catalyst, for instance one containing 4 to 10% ofsulphur by weight of nickel, for the simultaneous hardening andisomerisation, or for a post-hardening isomerisation where this isrequired. Alternatively isomerisation can be effected before hardening.Palladium catalyst of satisfactory selectivity can also be used.Hydrogenation temperatures of 175 to 200 C. and pressures of about 1 to6 atmospheres are generally convenient with a sulphurised nickelcatalyst. Hydrogenation is preferably continued until polyethenoic acidhas been substantially eliminated, as indicated by the iodine valuereached in relation to the original acid content of the oil.

In most natural oils, especially vegetable oils, there is an unsaturatedacid radical at the 2-position of their glycerides: on selectivehydrogenation of such an oil containing polyethenoic acids up to thepoint where all polyethenoic acids have been converted to monoethenoicacids there is little increase in the saturated fatty acid content, andtherefore the proportion of unsaturated fatty acid radicals at the2-position is substantially undiminished.

6 Hence all that is necessary to ensure that a fat component A or B hasat least 85% of the 2-positions occupied by a C monoethenoic acidradical is to take an appropriate starting material and selectivelyhydrogenate it to the required extent.

The fractionation of fats is also a well-known process: in the form ofwet-fractionation known as solvent fractionation, fats are fractionallycrystallised from a suitable solvent, for instance acetone; the softerfractions (oleines) composed of the lower melting glycerides remainbehind in the solvent while the harder fractions (stearines) crystalliseor precipitate in liquid form and are separated off.

Fat components A can be prepared from palm, olive, cottonseed,groundnut, safiiower, sunflower, maize, and zero-erucic rapeseed oils,for example; and fat components B can be prepared from rapeseed oil ofadequate C and C fatty acid content, or from other crucifera oils, forinstance crambe oil (the oil from Crambe abyssinica): the preparation offat components B in general is described in US. patent specificationSer. No. 749,970 filed Aug. 5, 1968 and now abandoned.

In another form of the process of the invention the blend is formed bypreparing a mixture of suitable precursors of the fat components A and Bsuch as those mentioned above and submitting it to an isomerisationand/or selective hydrogenation step to form the blend of fat componentsA and B in situ. The nature and relative proportions of fat components Aand B in the product can be determined from the nature of the startingmaterials. The selective hydrogenation of the precursor mixturegenerally proceeds in the manner expected from the behaviour of theprecursors in separate hydrogenations.

It is to be understood that where the blend is made either by directmixing or by mixing precursors and hydrogenating, the fat components Aand B can each arise from two or more natural fats or fat fractions. Theseveral ingredient fats can be brought together in any order eitherbefore or after hydrogenation, and all that is necessary is that thefinal blend formed should meet the composition requirements of theinvention.

A product of a process of the invention can be further upgraded byfractionation if desired.

The invention includes an edible fat composition which contains less 10%of polyethenoic acids by weight (of total fatty acids), from 25 to 55%of C and C monoethenoic acids, at least 35% of C and C acids, at least85% of the acid residues at the 2-position of its triglycerides beingderived from C monoethenoic acid, the fat composition having dilatationsof at least 1050 at 20 C. and less than 200 at 35 C., a trans index ofbetween 40 and 60, an iodine value of between 50 and 80, and whosestable polymorphic form is beta prime. Preferably at least andespecially at least of the C and C acids is C acid, and preferably theiodine value is between 60 and 76.

The invention is illustrated by the following examples and theisodilatation diagrams shown in FIGS. 1 to 7 of the accompanyingdrawings; temperatures are in C., and amounts of fatty acids in percentby weight of total fatty acids. The fat components A and B in eachinstance had at least of the 2-positions of their glycerides occupied bya C monoethenoic acid radical.

EXAMPLE 1 Preparation of fat component A1 A palm oleine fraction ofiodine value 65.7 obtained by the solvent fractionation of palm oil andhaving the composition shown in Table 1a below was selectivelyhydrogenated using a non-pyrophoric sulphurised nickel on kieselguhrcatalyst containing 43% of nickel and 6.8% of sulphur by weight ofnickel. The oil fraction parts by weight) and catalyst (0.5 part) werestirred together in a hydrogenation autoclave under nitrogen and heatedto hydrogen gas was then introduced from the bottom of the vessel intothe mixture stirred at 500 r.p.m.,

with replacement of the nitrogen by venting o'fi and then operation ofthe hydrogenation autoclave as a dead end system. Hydrogen was rapidlyintroduced until a pressure of 34 lbs/in. was attained, and hydrogenflow into from 10 to 40% A1 correspond to the main part of the peak. Themaximum corresponds to the steepest dilatation curve. The latent heatdata indicate a similar maximum. The polymorphic form of the 25% A1:75%B1 the vessel then adjusted to maintain this pressure. Small freshlycrystallised composition was also shown to be samples of oil wereremoved by bleeding from time to beta prime. time and their iodine valueand slip melting point de- EXAMPLE 2 termined The aim oleine fraction ofExam 1e 1 40 arts b Hydrogenation was discontinued after 5 hours, whenweighopand the rapeseed oil of Exa H5316 1 g the 9 value thefiltered andfooled i 10 weight) were mixed and the mixture selectively hydro- 31 g pmm a 33 11 332 2 genated for 6 hours by the process described in Example6 ar i was W 1, to give a fat composition of the invention whose charitstrans index determined, and its fatty acid content acteristics were asfonOWS analysed: the results are given in Table la. X-ray powderdiffraction measurements showed that the fat crystallised 15 in thestable beta prime form.

Preparation of fat component B1 Dflatamns A bleached and refined Danish(summer p) p f 1t7i{%%. :.:::::::::::::::::::::B3 tit seed oil of acidvalue 0.1, saponification value 174 and Stable polymorphic form, betaprime {g 5 iodine value 103.7 and compositions shown in Table 1a wasselectively hydrogenated in the same way as the palm oleine fractionuntil in 5 hours it gave a hardened oil of the characteristics shown inTable la. X-ray measure- The dilatation values show that the product wassimiments showed that this fat crystallised in the beta prime lar to the40% Al, 60% B1 blend of Example 1, indipolymorphic form, but that thisslowly changed to the eating that mixing of precursor oils followed byhydrostable beta form. genation is equivalent to separate hydrogenationfollowed TABLE 1a by mixing. Palm oleine Rapeseed EXAMPLE 3 fractionCompooi1 Compog nip: ne r u b The palm oleine fraction of Example 1 (25parts by n r Weight) and the rapeseed oil of 'Example 1 (75 parts) 3 11x iu 05.7 103.7 were mixed, and the mixture selectively hydrogenated forTrans index, eree'nt :::III: IIIIII: 06 2 hours by the process describedin Example 1, to give a g 1 370 fat composition (a). Further products(b) and (c) were 115 made similarly except that hydrogenation wasmaintained D g for 3 hours and 3 /2 hours respectively. The products hadFatty acids: the following characteristics.

Saturated:

0 0 0.4 1.3 (a) (b) (c) Du ati roihyd'o e at (l 2 3 3 5 3 g -3 3:? 8 Ioine ame..uiif nf u fnn- 71.2 70.2 69:2 CQUIHOIIOBHG" 0 0 8.1 8.1 gig g gCrzmonoene 0 0 46.4 45.1 Dim 1 310 1 450 1 480 D30. 375 575 '640Blending of fat components A and B gig: g g g Blends of the fatcomponents A1 and B1 were made by mixing them in varying proportions andtheir dilatation values at various temperatures were determined. The Tht M 1 f f th t d f latent heat of fusion L of various compositions wasdetere g g Orm o e crys a Se a mined by diiferential thermal analysis onsamples heated c was Gun 0 e e a Pnme to above for 1 hour, and thencooled in melting ice EXAMPLE 4 'for 90 minutes, and the polymorphicform F of compositions crystallised more than 3 weeks earlier was alsoprepailanonfffat component A2 determined. The results were as indicatedin Table 1b. A Cottonseed 11 0f lodlne value 105 and having the TABLE 1bProportions Dilatations L D30 D35 D40 D45 F 445 30 10 0 20.1 Beta. Do.

545 40 10 Beta plus beta prime.

635 85 10 Beta prime. 010 75 10 Do.

An isodilatation diagram was constructed as described above and is shownin FIG, 1. It shows a maximum at 25% A1:75% Bl composition at below 30,tending to shift to a composition with slightly increased Al contentcomposition shown in Table 4a was selectively hydrogenated in the sameway as the palm oleine fraction of Example 1, except that one part byweight of catalyst was used to 100 parts of oil, until in 6 hours itgave a (33%) at higher temperatures. Compositions containing hardenedoil of the characteristics shown in Table 4a.

Preparation of fat component B2 A second batch of the rapeseed oil ofExample 1 was selectively hydrogenated as described there, giving ahardened oil of the characteristics shown in Table 4a.

TABLE 45.

Cottonseed Component oil starting material A2 B2 Iodine value 105 62. 475. 2 Slip M.P., degrees 39. 6 33. 1 Trans index, percent 49 65Dilatations:

D n 1, 585 1, 355 D30 1,105 400 D35 605 15 D40" 1 130 D45 1O Fattyacids:

Saturated:

Cm 25. O 25. 1 3. 4 3.0 4. 5 1. 9 1.0 1.1 0.3 0 0 1. 3

0 0. 9 0 C18 Iuonoene 18. 9 62.5 38.1 C18 diene 51.0 5.5 2.1 015 triene0 0 0 C1 monoene 1. 0 0. 6 7. 0 C21 monoene O 0 45. 8 Stable polymorphicform (1) Beta l Beta prime.

Blending of fat components A and B Blends of the fat components A2 andB2 were made as before, with dilatations shown in Table 4b.

TABLE 41) Proportions Dilatations A2 B2 D20 D25 Dan D An isodilatationdiagram was constructed as described above and is shown in FIG. 2. Itshows a maximum at 30% A2:70% B2 composition at tending to shift to acomposition with slightly decreased A2 content at -35". Compositionscontaining from 10 to A2 cover the main part of the peak. The maximumcorresponds to the steepest dilatation curve. The polymorphic form ofthe freshly crystallised 30% A2:70% B2 composition was found to be betaprime, and this was found to be stable.

EXAMPLE 5 Preparation of fat component A3 A groundnut oil of iodinevalue 86.2 and having the composition shown in Table 5a was selectivelyhydrogenated in the same way as the palm oleine fraction of Example 1,except that 1 part by weight of catalyst was used to 100 parts of oil,until in 7 hours it gave a hardened oil of the characteristics shown inTable 5 a.

Preparation of fat component B3 A third batch of the rapeseed oil ofExample 1 was selectively hydrogenated as described there, giving after4 hours a hardened oil of the characteristics shown in Table 5a.

TABLE 5a Groundnut Component oil Starting material A3 B3 Iodine value86. 2 67. 7 75. 8 Slip M.P., degrees 36.0 32. 3 Trans index, percent 5065 Dilatations:

Blending of fat components A and B Blends of the fat components A3 andB3 were made as before, with dilatations shown in Table 5 b.

TABLE 5b Proportions Dilatations A3 B3 D20 D25 D30 D35 D40 Anisodilatation diagram was constructed as described above and is shown inFIG. 3. It shows a maximum at 20% A3:80% B3 composition at 20, tendingto shift to a composition with slightly increased A3 content (30%) at30-35". Compositions containing from 10 to 50% A3 cover the main part ofthe peak. The maximum corresponds to the steepest dilatation curve. Thepolymorphic form of the freshly crystallised 25% A3:75% B3 compositionwas found to be beta prime, and this was found to be stable.

EXAMPLE 6 Preparation of fat component A4 A zero-erucic rapeseed oil ofiodine value 113.0 and having the composition shown in Table 6a wasselectively hydrogenated in the same way as the palm oleine fraction ofExample 1, except that the pressure was 24 lbs./in. temperature was 200C., stirring speed was 300 rpm. and 1.5 parts by weight of catalyst wereused to 100 parts of oil, until in 9 /2 hours it gave a hardened oil ofthe characteristics shown in Table 6a.

The hardened oil (100 parts by grams-weight) and dry acetone (900 partsby cc.-volume) were mixed and heated to 40, then cooled to 10 during 15minutes, the mixture allowed to stand for 30 minutes, the crystallisedfat filtered olf and washed three times with acetone parts each time) at10: the washed crystals were heated to drive off most of the acetoneremaining, and the small amount of residual acetone was removed byheating in a vacuum still, giving in 36% yield a stearine fraction ofselectively hydrogenated zero-erucic rapeseed oil of the characteristicsshown in Table 6a.

Preparation of fat component B4 The selectively hydrogenated rapeseedoil B1 of EX- ample 1 was fractionally crystallised from acetone in asimilar manner, except only that cooling was effected in 6 minutes: theyield of stearine fraction was 60% and it had the characteristics shownin Table 6a.

TABLE 6a Zeroerucic Hardened Component rapeseed rapeseed oil oil A4 B4Iodine value 113.0 77. 3 70.0 72. 5 Slip M.P., degrees" 31. 9 45.0 35.0Trans index, percent 68 70 67 Dilatations:

D20 1, 080 1, 920 1,740 Dar 1, 850 1, 560 D30 300 1, 555 1, 105 80 725180 5 395 15 110 Fatty acids:

Saturated:

C 3. 8 5. 6. 4. 3 1. 1 5. 5 10. 3 2. 2 0. 2 0 1. 4 1. 7 C22 0 U 0 1. 7Unsaturated:

C monoene 0 0 0 0 62. 4 84. 9 76.3 35. 4 19. 8 3. 5 3. 9 0 12. 8 0 0 00 1. 0 1. 6 8. 8 C2: monoene 0 0 0 45. 9 Stable polymorphic form BetaBeta Blending of fat components A and B Blends of the fat components A4and B4 were made as before, with dilatations shown in Table 6b.

TABLE 61) Proportions Dilatations B4 D Dao D D D An isodilatationdiagram was constructed as described above and is shown in FIG. 4. Itshows a maximum at 25% A4:75% B4 composition: compositions containingfrom 10 to 50% A4 cover the main part of the peak. The polymorphic formof the freshly crystallised 25 A4:75% B4 composition was found to bebeta prime, and this was found to be stable.

EXAMPLE 7 Preparation of fat component A5 The selectively hydrogenatedcottonseed oil A2 of Example 4 was fractionally crystallised fromacetone by the procedure described for fat component A4 in Example 6,except that 100 parts by grams-weight of hardened oil to 500 parts bycc.-volume of acetone were used, cooling was from 40 to 0 in 40 minutes,and the washing acetone was at 0 and 120 parts were used for each wash.

The stearine fraction, obtained in 80% yield, had the characteristicsshown in Table 7a.

Preparation of fat component B5 The selectively hydrogenated rapeseedoil of Example 5 (fat component B3) was fractionally crystallised fromacetone using the procedure described for fat component A4 in Example 6,to give a stearine fraction in yield having the characteristics shown inTable 7a.

TABLE 7a Component Iodine value 60. 3 72.7 Slip M.P., degrees 42. 7 34.2Trans index, percent 50 66 Dilatations:

26. 7 4. 8 6.0 2. 3 1. 2 1.1 C22 0 1.1 Unsaturated:

C10 11101108119 0 8 0 C monoene- 62. O 34. 1 01s diene 2. 7 0 C1 monoene0. 6 8. 6 C22 monoene 0 48. 0 Stable polymorphic form (1) Beta 1 Betaprime.

Blending of fat components A and B Blends of the fat components A5 andB5 were made as before, with dilatations shown in Table 7b.

TABLE 7b Proportions Dilatations B5 D20 D25 D30 D35 The isodilatationdiagram of FIG. 5 was constructed from these results. It shows a maximumat 25 A5; 75% B5 composition: compositions containing from 10 to 50% A5cover the main part of the peak. The polymorphic form of the freshlycrystallised 25% A5:75% B5 composition was found to be beta prime, andthis was found to be stable.

EXAMPLE 8 Preparation of fat component B6 A neutral crambe oil of acidvalue 0.50, saponification value 169.4, iodine value 95.3 and fatty acidcomposition shown in Table 8a was selectively hydrogenated under theconditions described for the palm oleine fraction of Example 1.Hydrogenation was completed in 7 hours and the hardened oil had thecharacteristics shown in Table 8a.

The hardened oil was fractionally crystallised from acetone using theprocedure described for fat component A4 in Example 6, to give astearine fraction in 60% yield having the characteristics shown in Table8a.

TABLE 89.

Starting Hard- Fat compomaterial ened oil nent B6 Iodine value 95. 3 74.6 72. 4 Slip M.P., degrees--- 33.0 37. 0 Trans index, percent 63Dilatations:

Dm 1, 345 1, 770 Dan 1, 675 1).. 460 1, 220 D 70 395 D40 5 45 Fattyacids:

Saturated:

O 2. 8 2. 8 2. 7 0. 8 1. 3 1. 7 0.3 0. 3 1.3 C22 0. 5 2. 4: 3. 9Unsaturated:

Cw monene 0.7 (In monoene. 15. 9 32. 6 30. 2 C15 diene. 10.2 1. 6 1. 5C18 tr1ene. 7. 8 0 0 C20 monoene. 4. 8 3. 3 3. 8 C22 monoene 56. 8 55. 554. 2 Stable polymorphic form Beta Blending of fat components A and BBlends of the fat components A4 (see Example 6) and B6 were made asbefore, with dilatations shown in Table 8b.

TABLE 8b Proportions Dilatations A4 B6 D D D Preparation of fatcomponent A6 A second batch of the palm oleine fraction of Example 1 wasselectively hydrogenated as described there, except that thehydrogenation temperature was 180, giving after 5 hours a hardened oilof the characteristics shown in Table 9a.

Preparation of fat component B7 An oleine fraction obtained by acetonefractionation of a selectively hardened rapeseed oil, and having thecharacteristics shown in Table 9a, was selectively hydrogenated by theprocedure described in Example 1 for fat component A1 except that 1 partof the catalyst to 100 parts of oil were used and the temperature was185". The hardened product obtained after 2 hours hydrogenation had thecharacteristics shown in Table 9a.

TABLE 9a Hardened rapeseed Compooleine Compo nent A6 fraction nent B7Iodine value 53. 5 81. 0 75. 8 28.0 32. 7 53 62 Saturated:

31. 8 3. 6 3.3 5. 3 1. 1 3. 2 0. 2 0. 3 1. 5 C22 0 0. 8 3. 2Unsaturated:

C 5 monoene 0 0. 3 C15 monoene 61. 6 31.0 27. 7 C15 diene 1.1 8.2 5. 6C2 monoene 0 10. 5 9. 4 C22 monoene O 45. 0 45. 6

Blending of fat components A and B Blends of the fat components A6 andB7 were made as An isodilatation diagram was constructed as describedabove and is shown in FIG. 7. It shows a maximum at 15% A6:85% B7composition, with the main part of the peak corresponding to from 10 to22% A6.

The edible fats produced by a process of the invention can be used assubstitutes for chocolate fats, in toffees, cake coatings and biscuitfilling creams. Thus a chocolate material can be made by formulating theproduct with suitable flavouring, for instance cocoa powder, sugar, milkpowder, and lecithin. Suitable formulations of products illustrated bythe edible fat products of Example 3 are as follows:

Parts by wt. Formulation A (milk chocolate):

Edible fat (b) of Example 3 35.5 Cocoa powder (containing 1'0-12% cocoa--butter) S Icing sugar 43 Skim milk powder 16.5 Lecithin 0.45Formulation B (milk chocolate):

Edible fat (b) of Example 3 30 Cocoa powder (containing 1012% cocoa Weclaim:

1. A process for preparing an edible fat composition, comprising bycontacting in the liquid state (a) from 10 to 50% by weight of anunrandomised fat component A the total fatty acids of whosetriglycerides have a C and C acid content of at least 90% by weight, ofwhich from 10 to 45% is saturated fatty acid, and (b) from 90 to 50% ofan unrandomised fat component B the total fatty acids of whosetriglycerides have a C and C acid content of from 30 to 75% by Weightand not more than 20% of saturated fatty acid, both components A and Bhaving at least of the 2-positions occupied by a C monoethenoic acidradical, and a trans index of between 40 and 75.

2. A process according to claim 1, where the fat component A has from 15to 40% of saturated C and C acids.

3. A process according to claim 2, where the fat component B has atleast 50% of C and C acids.

4. A process according to claim 3, where at least 75% of the total C andC acids in the fat component B is C22 acid.

5. A process according to claim 3, where the fat component A has notmore than 6% of saturated fatty acids other than C and C acids.

6. A process according to claim 3, where the fat component B has lessthan 12% of saturated fatty acid.

7. A process according to claim 6, where the fat component A has a transindex of between 40 and 60 and an iodine value of between 50 and 75.

8. A process according to claim 7, where the fat component B has a transindex of between 50 and 70, and an iodine value of between 65 and 80.

9. A process according to claim 8, where the total fatty acids of thefat components A and B contain less than 5% of polyethenoie acids.

10. -A process according to claim 8, where the fat component B is oneprepared from rapeseed or crambe oil.

11. A process according to claim 10, where the fat component A is oneprepared from palm, cottonseed, groundnut or zero-erucic rapeseed oil.

12. A process according to claim 1, where the stable polymorphic form ofthe fat component B is beta and that of the fat component A is betaprime.

13. A process according to claim 1, in which the proportion of fatcomponent A in the blend is such that the stable polymorphic form of theblend is beta prime.

14. An edible fat composition prepared by contacting in the liquid state(a) from to 50% by weight of an unrandornised fat component A the totalfatty acids of whose triglycerides have a C and C acid content of atleast 90% by weight, of which from 10 to is saturated fatty acid, and(b) from 90 to of an unrandomised fat component B the total fatty acidsof whose 16 triglycerides have a C and C acid content of from 30 to byweight and not more than 20% of saturated fatty acid, both components Aand B having at least of the 2-positions occupied by a C monoethenoicacid 5 radical, and a trans index of between 40 and 75.

References Cited UNITED STATES PATENTS 2,972,541 2/19'61 Cochran et al99118 H 3,361,568 1/1968 Kidger 99-118 H JOSEPH M. GOLIAN, PrimaryExaminer US. Cl. X.R. 15 99-118 H

